Sciencemadness Discussion Board

Interesting patent

Ritter - 4-8-2008 at 08:14

This recent patent presents the preparation of some intersting high-N compounds http://www.pat2pdf.org/patents/pat7375221.pdf including the following:

azidoaminotriazole
nitrosoguanazine
nitrosoguanazine dimer
azidoaminotriazole salts

Here is an OCR scan of the procedure from Example 1:
Quote:
Example 1

The Method of Making Azidoaminotriazole (5-azido-2H-[1,2,4]triazol-3-ylamine)(4) from Guanazine ([1,2,4]triazole-3,4,5-triamine) (1)

In an exemplary embodiment of the present invention, guanazine (1) (approximately 0.90 g, 7.9 mmol) may be dissolved in about 18 ml of distilled water at 23° C. and the resulting solution then stirred and cooled in an ice bath. Sodium nitrite (approximately 0.54 g, 7.9 mmole) may then be added. After the sodium nitrite dissolves, a solution of acetic acid (approximately 1.50 g, 25 mmole) in about 6 ml of distilled water may be slowly added, dropwise over about 30 minutes. The solution may be held at an ice bath temperature for about one hour before it is allowed to warm to about 22° C. over about one and a half hours. After about 30 minutes at about 22° C., a red-orange precipitate may be removed by filtration and washed twice with about 2 ml of water. The red-orange precipitate may weigh approximately
0.38 g after air-drying. The fltrate may then be extracted 3x with about 20 ml of ethyl acetate. The solvent may be removed from the combined ethyl acetate extracts to give approximately 0.36 g (approximately 37% yield) of azidoaminotriazole (4) (mp approximately 160-165° C., decomposition) that contained small amounts of impurities by TLC and 'H NMR analyses. TLC: RF of (4)=0.63 (chloroform/methanol/acetic acid, 40/8/1, v/v/v as developer). See 1HNMR and 13C NMR in Example 3, below.
The red-orange precipitate may contain very little azidoaminotriazole (4) by TLC analysis. The main component may be a yellow by-product that may be extracted into hot methanol. This yellow by-product may precipitate as a methanol solvate upon cooling. The yellow by-product has a melting point of about 160° C., with very rapid decomposition. Other analytical values of the yellow by-product may be as follows: TLC: R, 0.30 (chloroform/methanol/ acetic acid, 40/8/1, v/v/v as developer); IR (ATR): 35003800, 2141 (medium), 1360,1327 (medium strong), 1209 (strong) cm-'; 'H NMR (DMSO-d6): 5.80 (s, 2H), 6.37 (s, 2H), 12.38 (s, 1 H), 12.81 (s, 1 H) with peaks for methanol at
3.15 and 4.09; and 13C NMR (DMSO-d6): 152.5, 156.0,
162.1 (broadened) with a peak for methanol at 49.0.



The starting point is guanazine. See this pdf its preparation:http://www.sciencemadness.org/talk/viewthread.php?action=att...

My ChemDraw 11.0 says the nomenclature for the dimer is
(E)-1,4-bis(4,5-diamino-4H-1,2,4-triazol-3-yl)tetraaz-2-ene 2,3-dioxide and it is 68.5% N. The E/Z geometry opens up the possibility for crystalline polymorphs with different chyemical & physical properties, such as color.















[Edited on 4-8-2008 by Ritter]

Nitrosoguanazine.jpg - 32kB

Ritter - 5-8-2008 at 11:06

Again on the topic of recent patents for high-N energetic compounds, the triazolyl-tetrazinyl-aminotriazine salts & their chemistry is very interesting, if somewhat beyond the capabilities of the typical amateur chemists (reagents like hydrazine hydrate & cyanogen bromide). See http://www.pat2pdf.org/patents/pat6673924.pdf and http://www.pat2pdf.org/patents/pat6632305.pdf.

The prep of the intermediate 2,4-dichloro-6-hydrazino-s-triazine is found in this patent http://www.pat2pdf.org/patents/pat3061605.pdf

The story behind the earlier mistaken identity of the starting 1,2,4-triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine precursor is an interesting story.

The anion of the aminotriazine is 71+% N. The salts are stated to be 'platforms for novel explosive & pyrotechnic compounds'. I can think of all kinds of interesting things to do with this compound, such as making both the azide & the N-nitroso derivative & its dimer by analogy to the first post in this thread.

The revised attachment has been sized to 800x342 pixels using Irfanview.









[Edited on 6-8-2008 by Ritter]

triazoolyl-tetrazinyl-aminotriazine salt.gif - 27kB

Ritter - 7-8-2008 at 13:31

An alternate synthesis of the [1,2,4]triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine dcescribed in the post above is described in this patent under the non-systematic name of guanazoguanazole: http://www.pat2pdf.org/patents/pat2648671.pdf. It is formed as a co-product in the synthesis of guanazole from dicyandiamide (aka cyanoguanidine) & hydrazine hydrochloride in water by adding excess dicyandiamide. Yield is 83%. Apparently a molecule of ammonia is eliminated in this reaction.

Refs: http://article.pubs.nrc-cnrc.gc.ca/ppv/RPViewDoc?_handler_=H...

The previously posted thread URL for the guanazine prep no longer works for some reason.

Guanazole itself looks like it has a lot of potential for experimenting with higher N-content energetic derivatives: azides, N-nitroso derivatives, their dimers, etc.

Image edited to 800x139 pixels with Irfanview.




[Edited on 7-8-2008 by Ritter]

guanazoguanazole.gif - 14kB

Nick F - 8-8-2008 at 09:58

Treat that guanazoguanazole with HNO2 + CuSO4 and you should get something rather tasty, if your solution doesn't spontaneously detonate!

[Edited on 8-8-2008 by Nick F]

Ritter - 8-8-2008 at 10:42

Quote:
Originally posted by Nick F
Treat that guanazoguanazole with HNO2 + CuSO4 and you should get something rather tasty, if your solution doesn't spontaneously detonate!

[Edited on 8-8-2008 by Nick F]


Can you be more specific about your proposed reaction? What you are proposing is forming the diazonium salt & then decomposing it via the CuSO4 acting as a catalyst.

The_Davster - 8-8-2008 at 10:48

If excess nitrite was used in an analogous procedure to the synthesis of nitrotetrazole from aminotetrazole one could potentially isolate the dinitro compound.

Nick F - 8-8-2008 at 11:02

That's right, I was thinking of a Sandmeyer rxn.

Ritter - 8-8-2008 at 11:05

Quote:
Originally posted by The_Davster
If excess nitrite was used in an analogous procedure to the synthesis of nitrotetrazole from aminotetrazole one could potentially isolate the dinitro compound.


Are you referring to guanazole or guanazoguanazole?

If the latter, I think we're looking at differential reactivity as far as the 3 amino groups go. IIRC, the diazonium salt of the triazole amino group is isolated & then thermally decomposed to get the anion. I don't have any info on which of the 2 remaining amino groups will react first. But it appearas likely that you could make several different products from guanazoguanazole.

As far as guanazole goes, the dinitro derivative would be very interesting.

The_Davster - 8-8-2008 at 11:10

I was referring to guanazole.

I am not sure of the effects of diazotizing the guanazoguanazole, although my gut tells me conditions could be modified to introduce another high-nitrogen heterocyclic ring there, perhaps not a simple diazotization, but making another triazole through the amine groups should be possible.

[Edited on 8-8-2008 by The_Davster]

Ritter - 8-8-2008 at 11:20

Quote:
Originally posted by The_Davster
I was referring to guanazole.

I am not sure of the effects of diazotizing the guanazoguanazole, although my gut tells me conditions could be modified to introduce another high-nitrogen heterocyclic ring there, perhaps not a simple diazotization, but making another triazole through the amine groups should be possible.

[Edited on 8-8-2008 by The_Davster]


Here is a brief note on this prep: http://www.maik.ru/abstract/rjapchem/0/rjapchem0839_abstract...

And 3,5-dinitro-4H-1,2,4-triazole ammonium salt (ADNT) is indeed classified as a military explosive: http://www.pat2pdf.org/patents/pat4236014.pdf. The triazole ring becomes an anion:

[Edited on 8-8-2008 by Ritter]

ADNT.jpg - 5kB

Nick F - 8-8-2008 at 11:22

"As far as guanazole goes, the dinitro derivative would be very interesting."

"Several techniques for the preparation of the parent compound, 3,5-dinitro-1,2,4-triazole (DNT), have been reported in the literature, but the preferred method has been synthesis from 3,5-diamino-1,2,4-triazole (guanazole, DAT), sulfuric acid, and excess sodium nitrite."

Taken from United States Patent 4236014, which actually deals with the preparation of the ammonium salt.

the 3-amino-5-nitro compound has also been studied (ANTA), and is often prepared by reduction of DNT, eg with hydrazine.

3,5-Diazido-1,2,4-triazole

Ritter - 8-8-2008 at 12:34

U.S. Army study on candidate stab initiators:

http://www.serdp.org/Research/upload/PP-1364-FR-01.pdf

Here's info on one guanazole derivative that appears to be too sensitive to prepare & handle safely:

[Edited on 8-8-2008 by Ritter]

3,5-Diazido-1,2,4-triazole.jpg - 7kB

Ritter - 8-8-2008 at 12:52

Quote:
Originally posted by Nick F
"Several techniques for the preparation of the parent compound, 3,5-dinitro-1,2,4-triazole (DNT), have been reported in the literature, but the preferred method has been synthesis from 3,5-diamino-1,2,4-triazole (guanazole, DAT), sulfuric acid, and excess sodium nitrite."

Taken from United States Patent 4236014, which actually deals with the preparation of the ammonium salt.


That patent, as shown in the graphic I posted, does deal with the preparation of the 3,5-dinitro-1,2,4-triazole anion starting from guanazole. It is isolated as the ammonium salt. The only other patent I could find on the preparation of 3,5-dinitro-1,2,4-triazole employs the Sandmeyer reaction but starts from guanazine rather than guanazole. See http://www.pat2pdf.org/patents/pat3111524.pdf.



[Edited on 8-8-2008 by Ritter]

Engager - 11-9-2008 at 18:26

Does somebody actualy tried to synth guanazine? I suppose answer is no, i've tried to make it from thiosemicarbazide and mercury oxide. Reaction is real pain, mercuric compounds are highly toxic, and large ammounts are needed to produce small quantity of product, insoluble mercuric compounds are hard to filter. To make matters worse, guanazine is readily oxidized by air, and can't be separated from solution without distilling off solvent in vacuum. Crude product is heavily contaminated by mercuric sulfide particles witch can't be easily removed by filtering (passes through paper filter). After dissolving in isopropyl alcohol, dark orange-red solution is obtained, no precipitate crystallized on cooling.

Synthesis of guanazine is very complicated, especialy in significant ammounts, so this will be very hard to get dinitrotriazole in home lab. Dinitrotriazole can also be prepared from guanazole, however in this case it comes with 50% contamination by 5-nitrotetrazole, and products will be hard to separate from each other, guanazole also oxidised by air, but at least don't require work with highly toxic mercuric compounds.

Engager - 16-12-2009 at 13:21

Quote: Originally posted by Ritter  
An alternate synthesis of the [1,2,4]triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine dcescribed in the post above is described in this patent under the non-systematic name of guanazoguanazole: http://www.pat2pdf.org/patents/pat2648671.pdf. It is formed as a co-product in the synthesis of guanazole from dicyandiamide (aka cyanoguanidine) & hydrazine hydrochloride in water by adding excess dicyandiamide. Yield is 83%. Apparently a molecule of ammonia is eliminated in this reaction.


Actually there is a big trouble here. In Patent US 6673924 authors have established structure of product resulted from heating dicyandiamide and hydrazine hydrochloride and found that product is not [1,2,4]triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine as previously believed and marked on commercial grade chemical, but is actualy [1,2,4]triazolo[1,5-a][1,3,5] triazine-2,5,7-triamine (watch picture below to find what i mean).



So there is a big difference! Guanazoguanazole produced from dycyandiamide and hydrazine hydrochloride has different chemical and physical properties. As clearly seen on the structure "Guanazoguanazole" can't preform ring closure as [1,2,4]triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine does. So your "alternative" way is not a way but a dead end!

Anyway, i tried to make some guanazoguanazole from dicyandiamide and hydrazine dihydrochloride and got 75% yield. It is interesting to know what product can be obtained by diazotizing guanazoguanazole by HCl/NaNO2 or by sandmeyer reaction. This products should be different but i haven't found any refs about someone tried this stuff. Someone have any bright ideas about what products of such diazotations should be? Davster! What do you think?


[Edited on 16-12-2009 by Engager]

azidoformamidinium 3,5-dinitro-1,2,4-triazole

Rosco Bodine - 14-6-2011 at 18:08

Guanyl Azide may possibly form an interesting salt with 3,5-dinitro-1,2,4-triazole. I am uncertain how it may be done, but speculate it may be possible to first form the aminoguanidine salt of 3,5-dinitro-1,2,4-triazole as an
intermediate.

Attached are some references. Guanazole would be gotten from Dicyandiamide reaction with hydrazine as per US2648671. Hydrazine Sulfate could be converted to the Hydrazine Dihydrochloride via Calcium Chloride and filtering.

Guanazole (DAT) is diazotized to 3,5-dinitro-1,2,4-triazole as per the method described on page 13 of the Los Alamos technical report attached.

The DNT is neutralized with aminoguanidine bicarbonate or
a double decomposition of perhaps a soluble sodium DNT salt with a soluble aminoguanidine salt perhaps the nitrate,
may work.

Then the aminoguanidine 3,5-dinitro-1,2,4-triazole is converted to the azidoformamidinium 3,5-dinitro-1,2,4-triazole per the method used for conversion of aminoguanidine perchlorate to azidoformamidinium perchlorate. See Klapotke paper attached, regarding compound 4 page 3.

No search has been done for the speculated compound
azidoformamidinium 3,5-dinitro-1,2,4-triazole ....
existence and properties at this point unknown.

Perhaps this could be a "green primary" class material
or a candidate for investigation.

Attachment: US2648671_PREPARATION_OF_GUANAZOLE.pdf (84kB)
This file has been downloaded 1140 times

Attachment: Diazotization of Guanazole to Dinitro Triazole 00312939.pdf (1.5MB)
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Attachment: Aminoguanidine Perchlorate, Triaminoguanidine Perchlorate, Guanyl Azide Perchlorate.pdf (316kB)
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[Edited on 15-6-2011 by Rosco Bodine]

Rosco Bodine - 28-7-2011 at 20:31

See relevant further discussion concerning different nitrosation products of guanazole is continued in the sticky thread entitled:
5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...

The production of guanazole from cyanoguanidine and hydrazine is still valid but other products can be gotten
from different molar ratios of reactants and different temperatures.

Attached is the relevant journal article which is cited by
the above mentioned patent US6673924. The article shows that for the variant guanazole related derivative product to be obtained instead of guanazole as described by US2648671 different reaction conditions and molar proportions are operative. The patent US2648671 of Roemer
shows a 1:1 molar ratio of cyanoguanidine with hydrazine dihydrochloride produces guanazole essentially in quantitative yield. Roemer also mentions the effect of longer reaction time with excess cyanoguanidine leads to the condensation of the guanazole first product with the remaining cyanoguanidine to produce "guanazoguanazole",
the conditions for that reaction better described in the attached article. In the article the proportion of reactants is 2:1 molar ratio for the more complex reaction product of guanazole which first forms with the unreacted excess cyanoguanidine to provide a somewhat lower than quantitative 83% reported yield for the "guanazoguanazole".

There would seem to be some confusion about these similar and related yet different reactions, which the attached article should clarify.

Attachment: CHEMISTRY OF DICYANDIAMIDE. V. STRUCTURES OF GUANAZOLE AND PYRO-GUANAZOLES, AND REACTION OF DICYANDIAMIDE WITH 3-4RIIN0- (405kB)
This file has been downloaded 959 times

[Edited on 29-7-2011 by Rosco Bodine]

Boffis - 30-7-2011 at 01:43

@Rosco Do you have the other parts of CHEMISTRY OF DICYANDIAMIDE? It very interesting stuff with regard to other threads.

Boffis - 30-7-2011 at 02:28

Also could someone repost the link to the guanazine synthesis in Ritter's opening post? When I follow the link it tells me hat I don't have access to this forum... which forum?

solo - 30-7-2011 at 06:10

Synthesis of 3,4,5-Triamino-4H-1,2,4-triazole (Guanazine) and its 4-Arylideneamino Derivatives

Attachment: Synthesis of 3,4,5-Triamino-4H-1,2,4-triazole (Guanazine) and its 4-Arylideneamino Derivatives.pdf (245kB)
This file has been downloaded 996 times

Rosco Bodine - 30-7-2011 at 06:15

The four earlier articles I do not have but only requested the fifth one.


[Edited on 30-7-2011 by Rosco Bodine]

related cyanoguanidine reactions

Rosco Bodine - 31-7-2011 at 17:24

While I did not get the earlier 4 articles in that series, I did find some additional patents which may be of interest for similar reactions.

US2352944 Triazole Derivatives

US2456090 Novel Dicyandiamide Derivatives

US2480514 Resins of Formaldehyde and Cyanoguanidine Derivatives

Attachment: US2352944_TRIAZOLE_DERIVATIVES.pdf (196kB)
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Attachment: US2456090_PREPARATION_OF_NOVEL_DICYANDIAMI.pdf (132kB)
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Attachment: US2480514_PREPARATION_OF_INFUSIBLE_RESINS.pdf (306kB)
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Boffis - 31-7-2011 at 23:35

@Solo Thank you for that. Guanazine looks very tricky!